JPS63215719A - polyester acrylate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention has low viscosity, excellent workability and coating properties, and has excellent hydrolysis resistance and weather resistance upon curing.

This invention relates to a novel polyester acrylate resin that produces a polyester acrylate resin that has excellent strength and elongation, is strong, flexible, flexible, and has excellent adhesion and adhesion.

Conventional technology In recent years, many radiation-curable resin compositions have been developed and are being used in paints, adhesives, pressure-sensitive adhesives, binders for magnetic tapes, etc., and the range of their use is expected to further expand in the future. There is. Polyester acrylate resins made of polyester acrylate and polymerizable monomers are known to have various compositions. In other words, by controlling the type and composition of the raw materials polyhydric alcohol and polybasic acid, an almost infinite number of combinations are possible, and a wide range of properties and properties of the cured product can be selected. It is seen as promising because it has performance comparable to acrylate resins.

In recent years, when polyester acrylate is used in paints, adhesives, etc., applications that require flexibility and flexibility have become extremely common, and the cured film is also required to have excellent hydrolysis resistance and weather resistance. However, since the various physical properties of conventional polyester acrylates are not satisfactory, improvement thereof is strongly desired.

The purpose of the present invention is to have low viscosity, excellent workability, and coating properties, and when cured, to have excellent hydrolysis resistance and weather resistance, excellent strength and elongation, and to be strong, flexible, and pliable. According to the present invention, the above object is achieved by providing a novel polyester acrylate resin which produces a polyester acrylate resin which is rich in polyester resin and has excellent adhesion and adhesion. R1 and R'1 are hydrogen or methyl groups, Rz is a polyester polyol residue, and tsm is an integer of 1 to 3. O achieved by using a polyester acrylate characterized by being a polyester polyol residue containing a structural unit represented by (7I'' [where R3 is 0 representing a hydrocarbon residue]). By using a polyester containing , it is possible to obtain film properties that are even more excellent in hydrolysis resistance, weather resistance, and flexibility.

What is polyester acrylate in the present invention?

For example, it can be produced from polyhydric alcohol, polyhydric carboxylic acid, and acrylic acid or methacrylic acid, and has an ester bond in the polymer main chain and an acryloyl group or methacryloyl group at the polymer end. In the invention, R3 represents a hydrocarbon residue in the polyester acrylate containing a structural unit represented by ``in'' in the molecule,
This is derived from the dicarboxylic acid component during polyester production, and specifically includes aliphatic acids having 4 to 10 carbon atoms such as succinic acid, maleic acid, galtaric acid, adipic acid, pimelic acid, azelaic acid, and cepatic acid.・Dicarboxylic acid and phthalic acid.

It is a residue derived from an aromatic dicarboxylic acid having 8 to 20 carbon atoms such as terephthalic acid and isophthalic acid.

Although 3-methyl-1,5-bentanediol is an essential component in the above-mentioned structural unit, there is no problem in including other diol components as copolymerization components as long as the effects of the present invention are not impaired. Other diols include, for example, 1
, 4-butanediol, 1,6 hexanediol, 1,
Examples include diols such as 9-nonanediol and 2-methyl-1,8-octanediol. When copolymerizing these other diols, 3-methyl-1,
It is preferred that 5-bentanediol is present in a proportion of 20 molar or more, particularly 50 molar or more.

? Ha 1 fc Intramolecular K -OCH2CH2CHCH2CO
Specifically, the polyester acrylate containing the structural unit represented by -TE refers to poly(β-methyl-δ-valerolactone) polyol or a polyol mixture containing this, or a polyester acrylate containing β-methyl-δ-valerolactone as one component. In the present invention, a block or random copolymer obtained by ring-opening copolymerization may be reacted with acrylic acid, acrylic acid chloride, methacrylic acid, or methacrylic acid chloride. Copolymer 1, for example, obtained by ring-opening copolymerization of ε-caprolactone and β-methyl-δ-valerolactone, in which CHa 0 u -OCH2CH2CHCH2CO- groups are introduced randomly or in blocks into the molecule. 7'c
It is also possible to use a block copolymer of adipate polyester polyol and β-methyl-δ-valerolactone.

The structural unit derived from β-methyl-δ-valerolactone is preferably contained in the polyester in an amount of 30% by weight, more preferably 50% by weight or more.

By using the polyester acrylate containing the above-mentioned methyl branched C6 group in the molecule, the resulting composition has excellent overall hydrolysis resistance, solvent resistance, and flexibility, and at the same time, the pigment Dispersibility becomes particularly good. The above-mentioned structure of polyester has excellent pigment dispersibility because the odd-numbered carbons are arranged in a straight line, and because it has methyl branches, it has good quality, especially low-temperature flexibility, and has good adhesion to the substrate. Excellent sex as well.

The polyester acrylate of the present invention is preferably a polyester acrylate having an average molecular weight of 300 to 10,000. Note that the method for synthesizing polyester acrylate is not particularly limited, but the following method may be exemplified.

(1) Enteric hydrochloric acid reaction between acrylic acid or methacrylic acid chloride and polyester polyol (2)
Direct dehydration reaction of acrylic acid or methacrylic acid and polyester polyol (3) Transesterification of lower alkyl ester of acrylic acid or methacrylic acid to polyester polyol (4) Acid chloride of polyester monoacrylate derivative and acrylic acid or methacrylic acid Dehydrochloric acid reaction (5) A dehalogenation metal reaction in which acrylic acid chloride or methacrylic acid chloride is reacted at the end of ring-opening polymerization of a lactone containing β-methyl-δ-valerolactone.

It can be synthesized by a method such as

The polyester acrylate of the present invention has a high reactivity [IJ] and diacrylates such as 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and diethylene glycol diacrylate, and polyesters such as trimethylolpropane triacrylate and pentaerythritol triacrylate. It goes without saying that functional acrylates, monofunctional acrylates such as dicyclopentagenyl acrylate, and 2-ethylhexyl acrylate may be used in combination.

Further, in order to prevent radical polymerization of the produced polyester acrylate, a radical polymerization inhibitor of about 0.001 to 0.05% by weight can be added to the system. Examples of the inhibitor include hydroquinone, hydroquinone monomethyl ether, etc.Means for curing the composition of the present invention include, for example, electron beam curing, ultraviolet curing, thermosetting, and other known methods. can also be adopted.

When curing the composition of the present invention with ultraviolet light, a photoinitiator as shown below is added. Specific examples include benzophenone% p-methoxybenzophenone, acetophenone, globiophenone, xanthone, benzoin, benzoin ethyl ether, anthraquinone, naphthoginone, etc., and the amount thereof is about 0.1% based on the polyester acrylate contained in the composition. ~1
Add about 5% by weight. At this time, a photoactive agent such as methylamine, jetanolamine, N-methyljetanolamine, or tributylamine may be added.

When the composition of the present invention is cured by heat, known radical polymerization initiators such as hydrogen peroxide, benzoyl peroxide, cumene peroxide, t-butyl hydroperoxide, azobisbutyronitrile, etc. are used. be able to.

When curing by electron beam irradiation, addition of a photoinitiator, a radical polymerization initiator, etc. is not particularly required.

Regardless of which of these curing methods is adopted, the polyester acrylate obtained by the present invention has properties that have not been previously available such as toughness, corrosion resistance, weather resistance, flexibility, adhesion, and adhesion. Provides a cured product with properties. Furthermore, the internal strain caused by volume shrinkage during curing is small, making it particularly useful as an adhesive.

5. In addition to the above-mentioned compounding agents, other additives may be added to the polyester acrylate of the present invention, within a range that does not impair the purpose of the present invention.
Conventional additives and fillers can be added depending on the purpose of use.

More specifically, the polyester acrylate obtained by the present invention is useful in paints, coatings, adhesives, inks, sealants, etc.

Examples In order to explain the present invention more specifically, the following examples are given below.
A comparative example will be given. In the examples, parts indicate parts by weight. The performance of the faeces coating film was determined by the following method.

(1) Adhesion: How many of the 100 test pieces were adhered using the method of peeling cellophane tape? /10
Indicated by 0.

(11) Flexibility: A rectangular test piece with a width of 5 m and a length of 10 G was bent along the outer periphery of a cylinder with a diameter of 2 strokes and evaluated by whether the coating was cracked or not.

0iD Water resistance: Appearance and adhesion of the outer coating layer after immersing the test piece in pure water at 40°C for 240 hours (1 above)
method) was evaluated.

6V) Weather resistance: Sunshine weather off the test piece.
The sample was kept in a thermostat for 600 hours, and the appearance and adhesion of the outer coating layer (method according to (i) above) were evaluated.

Example 1 3-Methyl-1,5-bentanediol920. Of.

Adipic acid 876f (diol/acid molar ratio 1.3/
1) Esterification was carried out under normal pressure while passing N2 gas and distilling condensed water at a temperature of about 210°C. When the acid value of the polyester became 0.3 or less, the degree of vacuum was gradually increased using a vacuum pump to complete the reaction. In this way, a polyester polyol (hereinafter referred to as polyester (a)) having a hydroxyl value of 56 and an acid value of 0.1 was obtained. This polyester (
A) was liquid at room temperature and had a molecular weight of about 2,000.

Next, 36 parts of acrylic acid and 0.4 parts of hydroquinone monomethyl ether were added to this polyester polyol 500f, and esterification was carried out at 180°C to obtain a polyester diacrylate.

In addition, when IH-NMR spectra were measured in deuterated chloroform solvent, tetramethylsilane (
3-methyl-1,5 in polyester based on TMS)
- Hydrogen of the methyl group of bentanediol is 0.8 ppm,
The hydrogen of the methylene group adjacent to the oxygen atom of 3-methyl-1,5-bentanediol is 4.0 ppm, and the hydrogen of the methylene group adjacent to the carbonyl of adipic acid is 2.2 ppm.
1 acrylic protons showed a resonance peak at 5.7-6.6 ppm.

Further, 100 parts of 1,6-hexanediol diacrylate and 350 parts of ethyl di[2-methacrylate phosphate were added to this polyester acrylate to obtain a polyester-based acrylate resin composition.

Obtained polyester acrylate resin composition 100
3 parts of benzoin ethyl ether to prepare a coating composition. This was applied onto an aluminum plate with a 75 micron applicator and irradiated with a high-pressure mercury lamp with an output of 80 W/m. The 0 coating film became tank-free by irradiating twice at a speed of 6 m/min, and was completely completed after 94 irradiations. A coating film irradiated six times was used to measure the cured Q physical properties.Examples 2 to 7 Polyester acrylate was obtained with the composition shown in Table 1 using the same molar ratio and the same method as in Example 1. Adipic acid/Isophthalic acid = 1/1 (molar ratio), Azelaic acid/Isophthalic acid = 1/1 (molar ratio), 3-methyl-1
, 5-bentanediol/1,6-hexanediol=
1/1 (molar ratio) Comparative Examples 1 to 3 Polyester acrylate was obtained with the composition shown in Table 1 using the same molar ratio and the same method as in Example 1.0 Example 8 Stirring device, dropping funnel, and gas Contents 1 with entrance/exit
After thoroughly purging the three-piece flask with dry nitrogen gas, the flask was immersed in a 0°C path, and 400 r of toluene (prepared by dehydration with sodium) was added to the flask.
Ll, ethylene glycol 42 and butyl lithium (
10.4 mol of 7 hexane (1 t) was charged and stirred for about 5 minutes. Then, pre-dehydrated and purified β-methyl-δ-valerolactone (128Pt) was added all at once from the dropping funnel. The viscosity also increased.After 1 hour, 21.6 d of acrylic acid chloride
was added dropwise into a syringe, and after 30 minutes, 400 d of water was added to the solution. The flask was returned to room temperature and after 5 minutes, the washing operation was repeated three times with distilled water, the toluene and a trace amount of water were distilled off using a rotary evaporator, and the mixture was purified by molecular distillation, resulting in a colorless and transparent viscous solution. When liquid 140.09 was obtained, this liquid was analyzed by oGPC (Kölpermeation chromatography), and it was found to be an oligomer with a molecular weight of about 2000 and a distribution with one peak. The following was also observed in the 'H-NNR spectrum and infrared absorption spectrum.

The obtained polyester acrylate was evaluated in the same manner as in Example 1. O l juice NMR spectrum 5.7-6.6 PI) m Acrylic proton 4.1
5' PPm methylene proton 1.2-2.4p
l) m methylene and methine protons 1.85 p
I) m Methyl proton infrared absorption spectrum 1720-1730cyy+-" carbonyl group of ester bond% acrylic group at 1640cm-1, 1380
an-” shows the absorption derived from the methyl group.

Example 9 In Example 8, β-methyl-J-valerolactone and ε-kabu p were used instead of β-methyl-δ-valerolactone.
Polyester acrylate was obtained in the same manner as in Example 1, except that lactone (molar ratio 1:1) was used, and evaluated.

Effects of the Invention As described above, the present invention is industrially useful in that it discloses a polyester acrylate with excellent flexibility, film properties, adhesion, water resistance, and weather resistance.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 and R'_1 are hydrogen or methyl group, R_
2 represents a polyester polyol residue, and l and m represent integers of 1 to 3. ) is a polyester acrylate with a number average molecular weight of 300 to 10,000, and R_2 is in the molecule with the formula ▲,
There are chemical formulas, tables, etc. ▼ [I] [However, R_3 represents a hydrocarbon residue. ] Or, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] A polyester acrylate characterized by being a polyester polyol residue containing a structural unit represented by the following. (2) In the polyester polyol residue, [I]
The polyester acrylate according to claim 1, wherein the structural unit represented by the formula is contained in an amount of 20 mol% or more in the total structural units. (3) In the polyester polyol residue, [I]
The polyester acrylate according to claim 1, wherein the structural unit represented by: is contained in the total structural units in an amount of 50 mol% or more. (4) The polyester acrylate according to claim 1, wherein in the polyester polyol residue, the structural unit represented by [II] is contained in an amount of 30% by weight or more in the total structural units. (5) The polyester acrylate according to claim 1, wherein in the polyester polyol residue, the structural unit represented by [II] is contained in an amount of 50% by weight or more in all structural units.